Low dielectric constant organic dielectrics based on cage-like structures

ABSTRACT

A low dielectric constant material has a first backbone with an aromatic moiety and a first reactive group, and a second backbone with an aromatic moiety and a second reactive group, wherein the first and second backbones are crosslinked via the first and second reactive groups in a crosslinking reaction without an additional crosslinker, and wherein a cage structure having at least 10 atoms is covalently bound to at least one of the first and second backbone.

This application is a divisional of allowed application Ser. No.09/545,058, filed Apr. 7, 2000 now U.S. Pat. No. 6,509,415.

FIELD OF THE INVENTION

The field of the invention is low dielectric constant materials.

BACKGROUND OF THE INVENTION

Interconnectivity in integrated circuits increases with decreasing sizeof functional elements and increasing complexity. To accommodate thegrowing demand of interconnections, complex configurations of conductorsand insulators have been developed. Such configurations generallyconsist of multiple layers of metallic conductor lines embedded inmultiple layers of insulators, which are fabricated from one or severallow dielectric constant materials. The dielectric constant in suchmaterials has a very important influence on the performance of theintegrated circuit. Insulator materials having low dielectric constants(i.e. below 3.0) are especially desirable, because they typically allowfaster signal propagation, reduce capacitive effects and cross talkbetween conductor lines, and lower voltages to drive integratedcircuits.

One way of achieving low dielectric constants in the insulator materialis to employ materials with inherently low dielectric constants.Generally, two different classes of low dielectric constant materialshave been employed in recent years—inorganic oxides and organicpolymers. Inorganic oxides, which may be applied by chemical vapordeposition or spin-on techniques, have dielectric constants betweenabout 3 and 4, and have been widely used in interconnects with designrule larger than 0.25 μm. However, as the dimension of interconnectscontinue to shrink, materials with even lower dielectric constant becomemore desirable.

Since 1998 integrated circuits with 0.25 μm design rule have been inproduction, but will be superseded by the production of the 0.18 μmgeneration ICs in 1999, and materials having dielectric constants lowerthan 3.0 are needed immediately. As the trend to even smaller designrules continues, design rules smaller than 0.18 μm are being developed,and design rules of 0.07 μm and below can be expected in just a fewgenerations, suggesting a strong need for dielectric materials withdesigned-in nanoporosity. Since air has a dielectric constant of about1.0, a major goal is to reduce the dielectric constant of nanoporousmaterials down towards a theoretical limit of 1, and several methods areknown in the art for fabricating nanoporous materials.

In some methods, the nanosized voids are generated by incorporation ofhollow, nanosized spheres in the matrix material, whereby the nanosizedspheres acts as a “void carriers”, which may or may not be removed fromthe matrix material. For example, U.S. Pat. No. 5,458,709 to Kamezaki etal., the inventors teach the use of hollow glass spheres in a material.However, the distribution of the glass spheres is typically difficult tocontrol, and with increasing concentration of the glass spheres, thedielectric material loses flexibility and other desirablephysico-chemical properties. Furthermore, glass spheres are generallylarger than 20 nm, and are therefore not suitable for nanoporousmaterials where pores smaller than 2 nm are desired.

To produce pores with a size substantially smaller than glass spheres,Rostoker et al. describe in U.S. Pat. No. 5,744,399 the use offullerenes as void carriers. Fullerenes are a naturally occurring formof carbon containing from 32 atoms to about 960 atoms, which is believedto have the structure of a spherical geodesic dome. The inventors mix amatrix material with fullerenes, and cure the mixture to fabricate ananoporous dielectric, wherein the fullerenes may be removed from thecured matrix. Although the pores obtained in this manner are generallyvery uniform in size, homogeneous distribution of the void carriersstill remains problematic.

In other methods, the nanosized voids are generated from a compositioncomprising a thermostable matrix and a thermolabile (thermallydecomposable) portion, which is either separately added to thethermostable matrix material (physical blending approach), or built-ininto the matrix material (chemical grafting approach). In general, thematrix material is first cured and crosslinked at a first temperatureT_(XL) to obtain a high T_(G) matrix, then the temperature is raised toa second temperature T_(T) (such that T_(T)<T_(G)) to thermolyze thethermolabile portion, and postcured at a third temperature (T_(C), withT_(C)<T_(G)) to form the desired nanoporous material having voidscorresponding in size and position to the size and position of thethermolabile portion. Continued heating of the nanoporous materialbeyond T_(C) will result in further annealing and stabilization of thenanoporous material.

In a physical blending approach, a thermostable matrix is blended with athermolabile portion, the blended mixture is crosslinked, and thethermolabile portion thermolyzed. The advantage of this approach is thatvariations and modifications in the thermolabile portion and thethermostable matrix are readily achieved. However, the chemical natureof both the thermolabile portion and thermostable matrix generallydetermine the usable window among T_(XL), T_(T), and T_(G) such thatT_(XL)<T_(T)<T_(G), thereby significantly limiting the choice ofavailable materials. Moreover, blending thermolabile and thermostableportions usually allows only poor control over pore size and poredistribution.

In the chemical grafting approach, a somewhat better control of poresize and pore distribution can be achieved when thermolabile portionsand thermostable portions are incorporated into a single blockcopolymer. The block copolymer is first heated to crosslink the matrix,further heated to thermolyze the thermolabile blocks, and then cured toyield the nanoporous material. Alternatively, thermostable portions andthermostable portions carrying thermolabile portions can be mixed andpolymerized to yield a copolymer, which is subsequently heated tothermolyze the thermolabile blocks. An example for this approach isshown in U.S. Pat. No. 5,776,990 to Hedrick et al. However, thesynthesis of block polymers having thermostable and thermolabileportions is relatively difficult and labor intensive, therefore addingsignificant cost. Furthermore, as the amount of thermolabile portions(i.e. porosity) increases, the nanoporous materials tend to collapsemore readily, thus limiting the total volume of voids that can beincorporated into the nanoporous material.

Although various methods are known in the art to introduce nanosizedvoids into low dielectric constant material, all, or almost all of themhave one or more than one disadvantage. Thus, there is still a need toprovide improved compositions and methods to introduce nanosized voidsin dielectric material.

SUMMARY OF THE INVENTION

The present invention is directed to low dielectric constant materialshaving a first backbone with an aromatic moiety and a first reactivegroup, and a second backbone with an aromatic moiety and a secondreactive group, wherein the first and second backbone are crosslinkedvia the first and second reactive groups in a crosslinking reactionpreferably without an additional crosslinker, and wherein a cagestructure having at least 10 atoms is covalently bound to at least oneof the first and second backbone.

In one aspect of the inventive subject matter first and second backboneare identical, preferably comprise a phenyl group, more preferablycomprise a poly(arylene ether), and most preferably comprise asubstituted resorcinol, a substituted tolane, or a substituted phenol asaromatic moiety. In other preferred aspects, the first and secondreactive groups are non-identical and comprise an ethynyl moiety or atetracyclone moiety, and the crosslinking reaction is a cycloadditionreaction.

In another aspect of the inventive subject matter the cage structurepreferably comprises a substituted or unsubstituted adamantane, orsubstituted or unsubstituted diamantane, wherein the adamantane ordiamantane may be incorporated into the backbone as a pendent group orsuch that the cage structure has a tetrahedral or polyhedralconfiguration.

Various objects, features, aspects and advantages of the presentinvention will become more apparent from the following detaileddescription of preferred embodiments of the invention, along with theaccompanying drawings in which like numerals represent like components.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a synthetic scheme to produce a low molecular weight polymerwith pendent cage structures according to the inventive subject matter.

FIG. 2 is a synthetic scheme to produce another low molecular weightpolymer with pendent cage structures according to the inventive subjectmatter.

FIGS. 3A-B are structures of various polymers according to the inventivesubject matter.

FIGS. 4A-B are synthetic schemes to produce various thermosettingmonomers according to the inventive subject matter.

FIGS. 5A-B are synthetic schemes to produce an end-capping molecule withpendent cage structures according to the inventive subject matter.

FIG. 6 is schematic structure of an exemplary low dielectric constantmaterial according to the inventive subject matter.

DETAILED DESCRIPTION

As used herein, the term “low dielectric constant material” refers toorganic, organometallic, and inorganic materials with a dielectricconstant of less than 3.0. The low dielectric material is typicallymanufactured in the form of a thin film of less than 100 μm, however,various shapes other than a film are also contemplated under the scopeof this definition, including thick films, blocks, cylinders, spheres,etc.

As also used herein, the term “backbone” refers to a contiguous chain ofatoms or moieties forming a polymeric strand that are covalently boundsuch that removal of any of the atoms or moiety would result ininterruption of the chain.

As further used herein, the term “reactive group” refers to any atom,functionality, or group having sufficient reactivity to form at leastone covalent bond with another reactive group in a chemical reaction.The chemical reaction may take place between two identical, ornon-identical reactive groups, which may be located on the same or ontwo separate backbones. It is also contemplated that the reactive groupsmay react with one or more than one exogenous crosslinking molecule tocrosslink the first and second backbones. Although crosslinking withoutexogenous crosslinkers presents various advantages, including reducingthe overall number of reactive groups in the polymer, and reducing thenumber of required reaction steps, crosslinking without exogenouscrosslinkers has also a few detriments. For example, the amount ofcrosslinking functionalities can typically be no more adjusted. On theother hand, employing exogenous crosslinkers may be advantageous whenthe polymerization reaction and crosslinking reaction are chemicallyincompatible.

As still further used herein, the term “cage structure” refers to amolecule having at least 10 atoms arranged such that at least one bridgecovalently connects two or more atoms of a ring system. The bridgeand/or the ring system may comprise one or more heteroatoms, and may bearomatic, partially saturated, or unsaturated. Further contemplated cagestructures include fullerenes, and crown ethers having at least onebridge. For example, an adamantane or diamantane is considered a cagestructure, while a naphthalene or an aromatic spirocompound are notconsidered a cage structure under the scope of this definition, becausea naphthalene or an aromatic spirocompound do not have one, or more thanone bridge.

In a preferred low dielectric constant material, the first and secondbackbone comprise a poly(arylene ether) with two pendent adamantanegroups, respectively, as cage structures as shown in Structures 1A-B(only one repeating unit of the backbone is shown). The first and secondaromatic moieties comprise a phenyl group, and the first and secondreactive groups are an ethynyl and a tetracyclone moiety, respectively,which react in a Diels-Alder reaction to crosslink the backbones.Preferred crosslinking conditions are heating the poly(arylene ether)backbones to a temperature of about 200° C.-250° C. for approximately30-180 minutes. Structure 1B can be synthesized as generally outlined inExample 1 below.

In alternative embodiments, the backbone need not be restricted to apoly(arylene ether), but may vary greatly depending on the desiredphysico-chemical properties of the final low dielectric constantmaterial. Consequently, when relatively high T_(G) is desired, inorganicmaterials are especially contemplated, including inorganic polymerscomprising silicate (SiO₂) and/or aluminate (Al₂O₃). In cases whereflexibility, ease of processing, or low stress/TCE, etc. is required,organic polymers are contemplated. There are many different appropriateorganic polymers, and some of the polymers may be especially suited forone purpose (e.g. low thermal coefficient of expansion), while otherpolymers may be especially suited for other purposes (e.g. superior gapfilling capability). Thus, depending on a particular application,contemplated organic backbones include aromatic polyimides, polyamides,and polyesters.

Although preferably built from low molecular weight polymers with amolecular weight of approximately 1000 to 10000, the chain length of thefirst and second polymeric backbones may vary considerably between five,or less repeating units to several 10⁴ repeating units, and more.Preferred backbones are synthesized from monomers in an aromaticsubstitution reaction, and synthetic routes are shown by way of examplein FIGS. 1 and 2. It is further contemplated that alternative backbonesmay also be branched, superbranched, or crosslinked at least in part.Alternatively, the backbones may also be synthesized in-situ frommonomers. Appropriate monomers may preferably include aromaticbisphenolic compounds and difluoroaromatic compounds, which may havebetween 0 and about 20 built-in cage structures.

It is especially contemplated that appropriate monomers may have atetrahedral structure, which are schematically depicted in Structures2A-B. In general Structure 2A, a thermosetting monomer has a cagestructure G, and at least two of the side chains R₁-R₄ comprise anaromatic portion and a reactive group, wherein at least one of thereactive groups of a first monomer reacts with at least one of thereactive group of a second monomer to produce a low dielectric constantpolymer. In general Structure 2B a cage structure, preferably anadamantane, is coupled to four aromatic portions which may participatein polymerization, and wherein R₁-R₄ may be identical or different.

When monomers with tetrahedral structure are used, the cage structurewill advantageously not only introduce a nanosized void, but alsocovalently connect four backbones in a three dimensional configuration.An exemplary monomer with tetrahedral structure and its synthesis isshown in FIG. 4B. It should further be appreciated that alternativemonomers need not be limited to compounds with a substituted orunsubstituted adamantane as a cage structure, but may also comprise asubstituted or unsubstituted diamantane, or fullerene as a cagestructure. Contemplated substituents include alkyls, aryls, halogens,and functional groups. For example, an adamantane may be substitutedwith a —CF3 group, a phenyl group, —COOH, —NO₂, or —F, —Cl, or —Br.Consequently, depending on the chemical nature of the cage structure,various numbers other than four aromatic portions may be attached to thecage structure. For example, where a relatively low degree ofcrosslinking through cage structures is desired, 1-3 aromatic portionsmay be attached to the cage structure, wherein the aromatic portions mayor may not comprise a reactive group for crosslinking. In cases wherehigher degrees of crosslinking is preferred, five and more aromaticportions may be attached to a cage structure wherein all or almost allof the aromatic portions carry one or more than one reactive group.Furthermore, it is contemplated that aromatic portions attached to acentral cage structure may carry other cage structures, wherein the cagestructures may be identical to the central cage structure, or may beentirely different. For example, contemplated monomers may have afullerene cage structure to provide a relatively high number of aromaticportions, and a diamantane in the aromatic portions. Thus, contemplatedcage structures may be covalently bound to a first and second backbone,or to more than two backbones.

With respect to the chemical nature of the aromatic portion it iscontemplated that appropriate aromatic portions comprise a phenyl group,and more preferably a phenyl group and a reactive group. For example, anaromatic portion may comprise a tolane, or a substituted tolane, whereinsubstituted tolanes may comprise additional phenyl groups covalentlybound to the tolane via carbon-carbon bonds, or carbon-non-carbon atombonds, including double and triple bonds, ether-, keto-, or estergroups.

Also contemplated are monomers that have pendent cage structures, asdepicted by way of example in FIG. 4A, in which two diamantane groupsare utilized as pendent groups. It should be appreciated, however, thatpending cage structures are not limited to two diamantane structures.Contemplated alternative cage structures include single and multiplesubstituted adamantane groups, diamantane groups and fullerenes in anychemically reasonable combination. Substitutions may be introduced intothe cage structures in cases where a particular solubility, oxidativestability, or other physico-chemical properties is desired. Therefore,contemplated substitutions include halogens, alkyl, aryl, and alkenylgroups, but also functional and polar groups including esters, acidgroups, nitro and amino groups, and so forth.

It should also be appreciated that the backbones need not be identical.In some aspects of alternative embodiments, two, or more than twochemically distinct backbones may be utilized to fabricate a lowdielectric constant material, as long as the alternative low dielectricconstant material comprises first and second backbones having anaromatic moiety, a reactive group, and a cage compound covalently boundto the backbone.

With respect to the reactive groups it is contemplated that manyreactive groups other than an tolanyl group and a tetracyclone group maybe employed, so long as alternative reactive groups are able tocrosslink first and second backbones without an exogenous crosslinker.For example, appropriate reactive groups include benzocyclobutenyl, andbiphenylene. In another example, a first reactive group may comprise anelectrophile, while a second reactive group may comprise a nucleophile.It is further contemplated that the number of reactive groupspredominantly depends on (a) the reactivity of the first and secondreactive group, (b) the strength of the crosslink between first andsecond backbone, and (c) the desired degree of crosslinking in the lowdielectric material. For example, when the first and second reactivegroups are sterically hindered (e.g. an ethynyl group between twoderivatized phenyl rings), a relatively high number of reactive groupsmay be needed to crosslink two backbones to a certain extent. Likewise,a high number of reactive groups may be required to achieve stablecrosslinking when relatively weak bonds such as hydrogen bonds or ionicbonds are formed between the reactive groups.

In cases where a reactive group in one backbone is capable of reactingwith an identical reactive group in another backbone, only one type ofreactive group may be needed. For example, tolanyl groups located on thesame of two different backbones may react in an addition-type reactionto form crosslinking structures.

It should also be appreciated that the number of reactive groups mayinfluence the ratio of intermolecular to intramolecular crosslinking.For example, a relatively high concentration of reactive groups in firstand second backbones at a relatively low concentration of both backbonesmay favor intramolecular reactions. Similarly, a relatively lowconcentration of reactive groups in first and second backbones at arelatively high concentration of both backbones may favor intermolecularreactions. The balance between intra- and intermolecular reactions mayalso be influenced by the distribution of non-identical reactive groupsbetween the backbones. When an intermolecular reaction is desired, onetype of reactive group may be placed on the first backbone, whileanother type of reactive group may be positioned on the second backbone.Furthermore, additional third and fourth reactive groups may be employedwhen sequential crosslinking at different conditions is desired (e.g.two different temperatures).

The reactive groups of preferred backbones react in an addition-typereaction, however, depending on the chemical nature of alternativereactive groups, many other reactions are also contemplated, includingnucleophilic and electrophilic substitutions, or eliminations, radicalreactions, etc. Further alternative reactions may also include theformation of non-covalent bonds, such as electrostatic bonds,hydrophobic bonds, ionic bonds and hydrogen bonds. Thus, crosslinkingthe first and second backbone may occur via a covalent or non-covalentbond formed between identical or non-identical reactive groups, whichmay be located on the same or two backbones.

In further aspects of alternative embodiments, the cage structure maycomprise structures other than an adamantane, including a diamantane,bridged crown ethers, or fullerenes, as long as alternative cagestructures have 10 or more atoms. The selection of appropriate cagestructures is determined by the desired degree of steric demand of thecage structure. If relatively small cage structures are preferred, asingle adamantane, or diamantane group may be sufficient. Exemplarystructures of backbones including adamantane and diamantane groups areshown in FIGS. 3A and 3B. Large cage structures may comprise fullerenes.It should also be appreciated that alternative backbones need not belimited to a single type of cage structure. Appropriate backbones mayalso include 2-5, and more non-identical cage structures. For example,fullerenes may be added to one or both ends of a polymeric backbone,while diamantane groups are placed in the other parts of the backbone.Further contemplated are derivatized, or multiple cage structures,including oligomerized and polymerized cage structures, where evenlarger cage structures are desired. The chemical composition of the cagestructures need not be limited to carbon atoms, and it should beappreciated that alternative cage structures may have atoms other thancarbon atoms (i.e. heteroatoms), whereby contemplated heteroatoms mayinclude N, O, P, S, B, etc.

With respect to the position of the cage structure it is contemplatedthat the cage structure may be connected to the backbone in variouslocations. For example, when it is desirable to mask terminal functionalgroups in the backbone, or to terminate a polymerization reactionforming a backbone, the cage structure may be employed as an end-cap.Exemplary structures of end-caps are shown in FIGS. 5A and B. In othercases where large amounts of a cage structure are desired, it iscontemplated that the cage structures are pendent structures covalentlyconnected to the backbone. The position of the covalent connection mayvary, and mainly depends on the chemical make-up of the backbone and thecage structure. Thus, appropriate covalent connections may involve alinker molecule, or a functional group, while other connections may be asingle or double bond. When the cage group is a pendent group it isespecially contemplated that more than one backbone may be connected tothe cage structure. For example, a single cage structure may connect2-3, and more backbones. Alternatively, it is contemplated that the cagegroup may be an integral part of the backbone.

It is still further contemplated that alternative low dielectricconstant material may also comprise additional components. For example,where the low dielectric constant material is exposed to mechanicalstress, softeners or other protective agents may be added. In othercases where the dielectric material is placed on a smooth surface,adhesion promoters may advantageously employed. In still other cases theaddition of detergents or antifoam agents may be desirable.

Turning now to FIG. 6, an exemplary low dielectric constant material isshown in which a first backbone 10 is crosslinked to a second backbone20 via a first reactive group 15 and a second reactive group 25, whereinthe crosslinking results in a covalent bond 50. Both backbones have atleast one aromatic moiety (not shown), respectively. A plurality ofpendent cage structures 30 are covalently bound to the first and secondbackbones, and the first backbone 10 further has a terminal cage group32. The terminal cage group 32, and at least one of the pendent cagegroups 30 carries at least one substituent R 40, wherein substituent 40may be a halogen, alkyl, or aryl group. Each of the cage structurescomprises at least 10 atoms.

EXAMPLES

The following examples describe exemplary synthetic routes forproduction of backbones having cage-like structures.

Example 1 Synthesis of 4,6-bis(adamantyl)resorcinol

Into a 250-mL 3-neck flask, equipped with nitrogen inlet, thermocoupleand condenser, were added resorcinol (11.00 g, 100.0 mMol),bromoadmantane (44.02 g, 205.1 mMol) and toluene (150 mL). The mixturewas heated to 110° C. and became a clear solution. The reaction wasallowed to continue for 48 h, at which time TLC showed that all theresorcinol had disappeared. The solvent was removed and the solid wascrystallized from hexanes (150 mL). The disubstituted product wasobtained in 66.8% yield (25.26 g) as a white solid. Another 5.10 gproduct was obtained by silica gel column chromatography of theconcentrated mother liquor after the first crop. The total yield of theproduct was 80.3%. Characterization of the product was by proton NMR,HPLC, FTIR and MS.

Incorporation of 4,6-bis(adamantyl)resorcinol into a poly(arylene ether)backbone

In a 250-mL 3-neck flask, equipped with a nitrogen inlet, thermocoupleand Dean-Stark trap, were added bis(adamantyl)resorcinol (7.024 g, 18.57mMol), FBZT (5.907 g, 18.57 mMol), potassium carbonate (5.203 g, 36.89mMol) and DMAC (50 mL), toluene (25 mL). The reaction mixture was heatedto 135° C. to produce a clear solution. The reaction was continued for 1h at this temperature and the temperature was raised to 165° C. byremoving some of the toluene. The course of polymerization was monitoredby GPC. At M_(w)=22,000, the reaction was stopped. Another 50-mL portionof DMAC was added to the reaction flask. The solid was filtered at roomtemperature, and was extracted with hot dichloromethane (2×150 mL).Methanol (150 mL) was added to the solution to precipitate a whitesolid, which was isolated by filtration. The yield was 65.8% (8.511 g).The solid was dissolved in THF (150 mL) and methanol (300 mL) was addedto the solution slowly. The precipitated white solid was isolated byfiltration and dried in vacuo at 90° C.

The synthetic procedure for backbone 1 follows the procedure asdescribed in Example 2, but employs 4,4′-difluorotolane as the difluorocompound.

Example 4 Contemplated Alternative Backbones

The following structures are contemplated exemplary backbones that canbe fabricated according to the general synthetic procedure in Examples 1and 2.

Example 5

This example demonstrates an exemplary synthesis for a thermosettingmonomer as depicted in FIG. 4B according to the inventive subjectmatter.

Synthesis of 1,3,5,7-tetrabromoadamantane

Tetrabromoadamantane synthesis started from commercially availableadamantane and followed the synthetic procedures as described in G. P.Sollott and E. E. Gilbert, J. Org. Chem., 45, 5405-5408 (1980), B.Schartel, V. Stümpflin, J. Wendling, J. H. Wendorff, W. Heitz, and R.Neuhaus, Colloid Polym. Sci., 274, 911-919 (1996), or A. P. Khardin, I.A. Novakov, and S. S. Radchenko, Zh. Org. Chem., 9, 435 (1972).Quantities of up to 150 g per batch were routinely synthesized.

Synthesis of 1,3,5,7-tetrakis(3/4-bromophenyl)adamantane

1,3,5,7-tetrakis(3/4-bromophenyl)adamantane was synthesized from1,3,5,7-tetrabromoadamantane following a procedure as describedelsewhere (V. R. Reichert and L. J. Mathias, Macromolecules, 27,7015-7023 (1994), V. R. Reichert, Ph. D. Dissertation, “Investigation ofderivatives and polymers of 1,3,5,7-tetraphenyladamantane,” Universityof Southern Mississippi, 1994). LC-MS was used to identify thecomponents of the isomeric mixture after the first synthesis. Treatingthe reaction product with fresh AlBr₃ catalyst favored the compositionof the isomeric mixture kinetically the one that was enriched in Ph4Br4isomer.

Synthesis of 1,3,5,7-tetrakis(3/4-tolanyl)adamantane

1,3,5,7-tetrakis(3/4-tolanyl)adamantane was synthesized from1,3,5,7-tetrakis(3/4-bromophenyl)adamantane by reacting1,3,5,7-tetrakis(3/4-bromophenyl)adamantane in triethylamine with anabout nine-fold molar excess of phenylacetylene in the presence of Pdcatalyst dichlorobis(triphenylphosphine)palladium[II] and copper[I]iodide for 4 hours at 80° C.

Example 6

Adamantanyl endcapped monomers as shown in FIGS. 5A and 5B weresynthesized as described in C. M. Lewis, L. J. Mathias, N. Wiegal, ACSPolymer Preprints, 36(2), 140 (1995).

Thus, specific embodiments, applications, and methods for producing lowdielectric constant dielectrics having cage-like structures have beendisclosed. It should be apparent, however, to those skilled in the artthat many more modifications besides those already described arepossible without departing from the inventive concepts herein. Theinventive subject matter, therefore, is not to be restricted except inthe spirit of the appended claims. Moreover, in interpreting both thespecification and the claims, all terms should be interpreted in thebroadest possible manner consistent with the context. In particular, theterms “comprises” and “comprising” should be interpreted as referring toelements, components, or steps in a non-exclusive manner, indicatingthat the referenced elements, components, or steps may be present, orutilized, or combined with other elements, components, or steps that arenot expressly referenced.

1. A low dielectric constant material, comprising: a first backbonehaving a first aromatic moiety and a first reactive group; a secondbackbone having a second aromatic moiety and a second reactive groupwherein the first and second backbones are crosslinked via the first andsecond reactive groups in a crosslinking reaction, wherein the reactionis a cycloaddition; and wherein at least one of the first or secondbackbones comprises at least one thermosetting monomer having theformula:

wherein G is a cage structure, and wherein R₁-R₄ comprises an alkylgroup, an aryl group, a halogen atom, CF₃, COOH, or NO₂, wherein atleast two of R₁-R₄ comprises an aromatic portion and a reactive group,and wherein the reactive group on the at least one thermosetting monomermay comprise the first reactive group or the second reactive group. 2.The low dielectric constant material of claim 1, wherein the cagestructure comprises at least one of an adamantane and a diamantane.
 3. Alayer comprising said low dielectric constant polymer of claim
 1. 4. Thelayer of claim 3, wherein said aromatic portion comprises phenyl.
 5. Thelayer of claim 3, wherein said cage structure comprises substituted orunsubstituted adamantane or substituted or unsubstituted diamantane. 6.A film comprising said low dielectric constant material of claim
 1. 7.The film of claim 6, wherein the thickness of the film is less than 100μm.
 8. The film of claim 6, wherein the dielectric constant is less than3.
 9. The film of claim 6, wherein said cage structure comprisessubstituted or unsubstituted adamantane or substituted or unsubstituteddiamantane.
 10. An insulator comprising said low dielectric constantmaterial of claim
 1. 11. The insulator of claim 10, wherein saidaromatic portion comprises phenyl.
 12. The insulator of claim 10,wherein said cage structure comprises substituted or unsubstitutedadamantane or substituted or unsubstituted diamantane.
 13. An integratedcircuit comprising the layer of claim
 3. 14. An integrated circuitcomprising the film of claim
 6. 15. An integrated circuit comprising theinsulator of claim 10.